Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
  • C09B62/24—Azo dyes
  • C09B62/245—Monoazo dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/022—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring the heterocyclic ring being alternatively specified
  • C09B62/026—Azo dyes
  • C09B62/028—Monoazo dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
  • D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group

Definitions

• This invention relates to fibre-reactive monoazo compounds and processes for their production. These compounds are suitable for use as fibre-reactive dyestuffs in any conventional dyeing or printing processes.
• the invention provides compounds of formula I ##STR2## and salts thereof, or a mixture of such compounds or salts, in which each R 1 is independently hydrogen, C 1-4 alkyl or substituted
• D is one of the radicals (a) to (f), ##STR3## in which R 2 is hydrogen, C 1-4 alkyl or C 1-4 alkoxy,
• R 3 is hydrogen, C 1-4 alkyl, carboxy or --O--A-- 1 --OR 4 ,
• a 1 is C 2-4 alkylene
• R 4 is hydrogen, sulpho, C 1-4 alkyl or C 2-4 hydroxyalkyl
• R 5 is C 2-4 alkyl
• R 6 is hydrogen or sulpho
• each R 7 is independently hydrogen, C 1-4 alkyl, C 1-4 alkoxy or carboxy;
• each p is 0, 1 or 2
• r is 1, 2 or 3
• each t is 0 or 1;
• each of Z and Z d is independently (z 1 ), (z 2 ) or (z 3 ), ##STR4## in which T 1 is hydrogen, chloro or cyano,
• each T 2 is fluoro or chloro
• Hal is fluoro or chloro
• B 1 is C 2-4 alkylene; --C 2-3 alkylene-Q--C 2-3 alkylene- in which Q is --O-- or --NR 1 --; C 3-4 alkylene monosubstituted by hydroxy, ##STR6## in which n is 0 or an integer 1 to 4,
• R 8 is hydrogen, C 1-4 alkyl, C 1-4 alkoxy, carboxy or sulpho, and the marked carbon atom is attached to the --NR 1 group which is bound to a carbon atom of the triazine ring;
• each of Z and Z 1 is independently (z 2 ) or (z 3 ), when D is a radical (d), (e) or (f), and at least one of Z and ##STR8##
• any alkyl, alkoxy or alkylene group present is linear or branched unless indicated otherwise.
• the hydroxy group is preferably bound to a carbon atom which is not directly attached to the nitrogen atom.
• Q is preferably bound to a carbon atom which is not directly attached to the nitrogen atom.
• R 1 is a substituted alkyl group, it is preferably monosubstituted by hydroxy, cyano or chloro.
• Each R 1 is preferably R 1a , where each R 1a is independently hydrogen, methyl, ethyl or 2-hydroxyethyl; more preferably each R 1 is R 1b , where each R 1b is independently hydrogen or methyl. Most preferably each R 1 is hydrogen.
• R 2 is preferably R 2a , where R 2a is hydrogen, methyl or methoxy.
• a 1 is preferably A 1 , where A 1 ' is C 2-3 alkylene.
• R 4 is preferably R 4a , where R 4a is hydrogen, sulpho, methyl, ethyl or C 2-3 hydroxyalkyl. More preferably, R 4 is R 4b , where R4b is hydrogen, sulpho or 2-hydroxyethyl.
• R 3 is preferably R 3a , where R 3a is hydrogen, methyl, carboxy or --O--A 1 '--OR 4a ; more preferably it is R 3b where R 3b is hydrogen, methyl or --O--A 1 '--OR 4b .
• R 5 is preferably R 5a , where R 5a is C 2-3 alkyl; most preferably R 5 is ethyl.
• R 6 is preferably hydrogen.
• Each R 7 is preferably R 7a , where each R 7a is independently hydrogen, methyl or methoxy.
• Hal is most preferably chlorine.
• R 8 is preferably R 8a , where R 8a is hydrogen, methyl, methoxy, carboxy or sulpho; more preferably it is R 8b , where R 8b is hydrogen or sulpho.
• B 1 is preferably B 1a , where B 1a , is C 2-3 alkylene, --CH 2 CH 2 --O--CH 2 CH 2 --, --CH 2 CH 2 --NR 1a --CH 2 CH 2 --, monohydroxy-substituted C 3-4 alkylene, ##STR9## in which n' is 0 or 1.
• B 1 is more preferably B 1b , where B 1b is C 2-3 alkylene, --CH 2 CH 2 --N 1b --CH 2 CH 2 --, --CH 2 CH(OH)CH 2 -- or ##STR10##
• B 1 is most preferably B 1c , where B 1c is --CH 2 CH 2 --, --CH 2 CH 2 CH 2 --, --*CH 2 CH(CH 3 )-- or --CH 2 CH(OH)CH 2 --, in which the marked carbon atom is bound to the --NR 1 group which is attached to a carbon atom of the triazine ring.
• W 1 is preferably W 1a , where W 1a is --NR 1a --B 1a --NR 1a --, ##STR11## more preferably it is W 1b , where W 1b is --NR 1b --B 1b --NR 1b -- or ##STR12## most preferably W 1 is W 1c , where W 1c is --NH--B 1c --NH--.
• (z 2 ) is preferably (z 2 ') or (z 2 ") of the formulae ##STR13## in which T 1 ' is hydrogen or chloro.
• (z 3 ) is preferably (z 3 ') of the formula ##STR14## in which Z 1 is a radical (z 2 ); more preferably it is (z 3 ") of the formula ##STR15## in which Z 1 ' is a radical (z 2 ') or (z 2 ").
• (a) is preferably (a') of the formula ##STR16## more preferably, R 3a in (a') is R 3b ; (b) is preferably (b') of the formula ##STR17## in which R 5a is most preferably ethyl; (c) is preferably (c') of the formula ##STR18## in which r' is 2 or 3; (d) is preferably (d') of the formula, ##STR19## in which the radical --(CH 2 ) t --NR 1b --Z d ' is in the meta- or para-position to the azo group,
• (e) is preferably (e') of the formula, ##STR20## and (f) is preferably (f') of the formula, ##STR21## in which the radical --(CH 2 ) t --NR 1b --Z d ' is in the meta- or para-position to --O--,
• radicals (d') to (f') Z d ' is a radical (z 2 ) or (z 3 ').
• Z d ' in a radical (d'), (e') or (f') is Z d ", where Z d " is a radical (z 2 '), (z 2 ") or (z 3 ").
• Preferred compounds of formula I correspond to formulae Ia, Ib and Ic, and salts thereof, ##STR22## in which D a is a radical (a') or (c'). More preferred are compounds of formula Ia, in which in (a') R 3 a is R 3b ; ##STR23## in which Z b is a radical (z 1 ) or (z 2 ), and the radical --NR 1a --Z b is in the 2- or 3-position of the naphthyl ring. More preferred are compounds of formula Ib in which
• R 1a is R 1b ;
• R 5a is ethyl
• the cation associated with the sulpho groups and any carboxy group is not critical and may be any one of those non-chromophoric cations conventional in the field of fibre-reactive dyes provided that the corresponding salts are water-soluble.
• examples of such cations are alkali metal cations and unsubstituted and substituted ammonium cations, e.g., lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, tri-ethylammonium and mono-, di- and tri- ethanolammonium.
• the preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.
• the cations of the sulpho and any carboxy groups can be the same or different, e.g., they can also be a mixture of the above mentioned cations meaning that the compound of formula I can be in a mixed salt form.
• the invention further provides a process for the preparation of compounds according to formula I or mixtures thereof, comprising reacting the diazonium salt of an amine of formula II,
• Diazotisation and coupling may be carried out in accordance with conventional methods; the coupling reaction is preferably carried out in a pH range of from 6.5-8.5, especially at pH 7-8.
• condensation of an amino group with a compound of formula Z-Hal is suitably carried out at a slightly elevated temperature in the range of from 35°-60° C., and at a pH of 4-6.
• the compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali metal salt, filtering and drying optionally in vacuo and at slightly elevated temperatures.
• a compound of formula I is obtained in free acid or preferably salt form or even mixed salt form containing, for example, one or more of the above mentioned cations. It may be converted from free acid form to a salt form or mixture of salt forms or vice versa or from one salt form to another by conventional means.
• any group Z or Z d which is a monofluoropyrimidinyl radical or a radical (z2) corresponding to the formulae ##STR31## can occur in two isomeric forms, with the floating fluoro or chloro substituent in either the 2- or the 6-position.
• the starting compounds of the formulae II, III and IV and also Z-Hal are either known or may be readily made from known starting materials by known methods using conventional diazotising, coupling and/or condensation reactions.
• the compounds of formula I and mixtures thereof are useful as fibre-reactive dyestuffs for dyeing or printing hydroxy group- or nitrogen-containing organic substrates.
• Preferred substrates are leather and fibre material comprising natural or synthetic polyamides and, particularly, natural or regenerated cellulose such as cotton, viscose and spun rayon.
• the most preferred substrate is textile material comprising cotton.
• Dyeing or printing is effected in accordance with known methods conventional in the fibre-reactive dyestuff field.
• the exhaust dyeing method is used at temperatures within the range of 30° to 80° C., particularly at 50°-60° C., whereby a liquor to goods ratio of 6:1 to 30:1 is used and more preferably of 10:1 to 20:1.
• the compounds of this invention have goqd compatibility with known fibre-reactive dyes; they may be applied alone or in combination with appropriate fibre-reactive dyestuffs of the same class having analogous dyeing properties such as common fastness properties and the extent of ability to exhaust from the dyebath onto the fibre.
• the dyeings obtained with such combination mixtures have good fastness properties and are comparable to those obtained with a single dyestuff.
• the compounds of formula I give good exhaust and fixation yields when used as dyestuffs. Moreover, any unfixed compound is easily washed off the substrate.
• the dyeings and prints derived from the compounds of formula I exhibit good light fastness and good wet fastness properties such as wash, water, sea water and sweat fastness. They also exhibit good resistance to oxidation agents such as chlorinated water, hypochlorite bleach, peroxide bleach and perborate-containing washing detergents.
• the suspension thus obtained is added all at once at 0°-5° to a diazonium salt solution which has been prepared in a conventional manner from 43.4 parts of 3-amino-4-methoxy-5-methylbenzene sulphonic acid.
• the pH of the reaction mixture is kept at 7.2-7.5 by the addition of 20% sodium carbonate solution.
• the formed dyestuff is salted out with sodium chlqride, filtered off and dried at 50° in vacuo.
• the dyestuff corresponds to the formula (shown in free acid form), ##STR32## it dyes cotton in orange shades. These cotton dyeings exhibit good light and wet fastness properties and are resistant to oxidative influences.
• the moist filter residue is dissolved in 300 parts by volume of 4% sodium hydroxide solution.
• the solution is refluxed at 90°-100° until the saponification of the acetamido groups is complete (which has to be monitored by thin layer chromatography).
• the reaction mixture is then cooled to 20° and the pH is adjusted to 4.3-4.8 by adding 30% hydrochloric acid. Subsequently, 26.8 parts of 2,4,6-trifluoropyrimidine are added.
• the pH of the mixture is kept at 4.3-4.8 by the continuous addition of 20% sodium carbonate solution, and the temperature is increased to 40°-45°.
• the dyestuff is salted out by adding sodium chloride, filtered and dried at 50° in vacuo. It corresponds to the formula (shown in free acid form) ##STR33##
• the compounds of Examples 3 to 96 may be applied to substrates which comprise cellulose fibres, and particularly to textile material comprising cotton using the conventional exhaust dyeing method or conventional printing processes, where dyeings or prints in orange to scarlet shades are obtained. These dyeings and prints on cotton show good properties with respect to light fastness and wet fastnesses and are resistant to oxidative influences.
• each marked carbon atom in the column under DT 2 is bound to the azo group in formula (T2); and each marked nitrogen atom in the column under --W 1 -- is bound to a carbon atom of the triazine ring in formula (T2).
• each marked carbon atom in the column under DT 4 is bound to the azo group in formula (T4); and each marked nitrogen atom in the column under --W 1 -- is bound to a carbon atom of the triazine ring in formula (T4).
• the suspension thus obtained is added all at once at 0°-50° to a diazonium salt solution which has been prepared in a conventional manner from 43.4 parts of 2-amino-5-ethoxybenzene sulphonic acid.
• the pH of the reaction mixture is kept at 7.0-7.5 by the addition of 15% sodium carbonate solution.
• the resultant dyestuff is salted out by the addition of sodium chloride, filtered and dried in vacuo at 50°.
• the dyestuff has the formula (shown in free acid form) ##STR94## and dyes cotton a scarlet-red shade. These cotton dyeings show good light- and wet-fastness properties and are resistant to oxidative influences.
• Examples 98 to 108 may be applied to substrates which comprise cellulose fibres, and particularly to textile material comprising cotton using the conventional exhaust dyeing method or conventional tional printing processes, where dyeings or prints in orange to scarlet-red shades are obtained. These dyeings and prints on cotton show good light- and wet-fastness properties and are resistant to oxidative influences.
• Example 1 By the preparation method described in Example 1, 2 or 97, the compounds of Examples 1-108 are obtained in their sodium salt form. By changing the reaction or isolation conditions or by using other known methods, it is possible to produce the compounds in the form of free acid or in other salt forms or mixed salt forms which contain one or more of the cations mentioned hereinabove.
• the exemplified dyestuffs contain two isomefic compounds regarding the radical ##STR97## one compound in which the floating fluoro substituent on the pyrimidine ring is in the 2-position and the corresponding compound wherein it is in the 6-position.
• the radicals ZT b , ZT c and ZT e are also present in two appropriate isomeric forms with respect to the floating chloro or fluoro substituent.
• the obtained mixtures of isomeric dyestuffs may be used in conventional dyeing or printing processes; the isolation of a single isomer for use normally is unnecessary.
• Example 1 0.3 Part of the dyestuff of Example 1 is dissolved in 100 parts of demineralised water and 8 parts of Glauber's salt (calcined) are added. The dyebath is heated to 50°, then 10 parts of cotton fabric (bleached) are added. After 30 minutes at 50°, 0.4 part of sodium carbonate (calcined) is added to the bath. During the addition of sodium carbonate the temperature is kept at 50°. Subsequently, the dyebath is heated to 60°, and dyeing is effected for a further one hour at 60°.
• the dyed fabric is then rinsed with running cold water for 3 minutes and afterwards with running hot water for a further 3 minutes.
• the dyeing is washed at the boil for 15 minutes in 500 parts of demineralised water in the presence of 0.25 part of Marseille soaps.
• a deep-orange cotton dyeing is obtained showing good fastness properties, and particularly high light- and wet-fastness properties, which is stable towards offdative influences.
• the dyed fabric is rinsed with running cold and then hot water and washed at the boil according to the method given in Application Example A. After rinsing and drying a deep-orange cotton dyeing is obtained which has the same good fastness properties as indicated in Application Example A.
• the dyestuffs of Examples 2-108 or mixtures of the exemplified dyestuffs may be employed to dye cotton in accordance with the method described in Application Example A or B.
• the cotton dyeings thus obtained are orange to scarlet and show good fastness properties.
• the printed fabric is dried and fixed in steam at 102°-104° for 4-8 minutes. It is rinsed in cold and then hot water, washed at the boil (according to the method described in Application Example A) and dried. An orange print is obtained which has good general fastness properties.
• the dyestuffs of Examples 2 to 108 or mixtures of the exemplified dyestuffs may be employed to print cotton in accordance with the method given in Application Example C. All prints obtained are orange to scarlet and show good fastness properties.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1993
  • 1993-09-14 CH CH2748/93A patent/CH685762A5/de not_active IP Right Cessation
  • 1993-09-15 FR FR9311077A patent/FR2695647B1/fr not_active Expired - Fee Related
  • 1993-09-15 IT ITRM930621A patent/IT1261709B/it active IP Right Grant
  • 1993-09-15 PT PT101365A patent/PT101365B/pt not_active IP Right Cessation
  • 1993-09-16 JP JP5230224A patent/JPH06207116A/ja active Pending
  • 1993-09-16 KR KR1019930018670A patent/KR100307696B1/ko not_active Expired - Fee Related
  • 1993-09-16 ES ES09301967A patent/ES2103169B1/es not_active Expired - Fee Related
  • 1993-09-16 GB GB9319209A patent/GB2270697B/en not_active Expired - Fee Related
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• 1996
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